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| 研究生： |
張家森 Chang, Chia-sen |
|---|---|
| 論文名稱： |
釕金屬催化雙炔與2,5-原冰片二烯反應製備冰片烯衍生物 Ruthenium-Catalyzed Cascade Reactions of Diynes with Norborandiene：Synthesis of new Norbornene Derivatives |
| 指導教授： |
吳耀庭
Wu, Yao-ting |
| 學位類別： |
碩士 Master |
| 系所名稱： |
理學院 - 化學系 Department of Chemistry |
| 論文出版年： | 2008 |
| 畢業學年度： | 96 |
| 語文別： | 中文 |
| 論文頁數： | 94 |
| 中文關鍵詞： | 原冰片二烯 、雙炔 、釕 |
| 外文關鍵詞： | ruthenium, diyne, norborandiene |
| 相關次數： | 點閱：72 下載：5 |
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3,4-二取代炔苊(3,4-diethynylacenaphthalenes) 20及庚二炔類化合物(1,6-heptadiynes) 32於釕錯合物催化下可與原冰片二烯(norbornadiene, 1)製備冰片烯衍生物[(5α,5aα,9aα,10α)-5,10-diphenyl-5,5a,6,9,9a,10-hexa -hydro-1H-6β,9β-naphtho[b,f:g]acenaphthalene, 21]和[(4α,4aα,8aα,9α)-4,9-diaryl 2,3,4,4a, 5,8,8a,9-octahydro-1H-5β,8β-methanocyclopenta[b] naphthalene, 36]，數種釕錯合物的催化效能、溶劑及添加物的影響已被測試，反應條件已調整至最佳化：原冰片二烯1及3,4-雙苯基炔苊(20a)溶於異丙醇與對二甲苯的混合溶液中加熱至130 oC，藉由釕錯合物的催化可產生原冰片二烯衍生物21a (74%)。依據此合成方法，數種冰片烯衍生物已被製備，產率為34-82%。藉由X-ray單晶繞射分析得知，此類反應具有位向選擇性，可以當作開環歧化的前驅物，未來可延伸製備高分子聚合物。
Reactions of 3,4-diethynylacenaphthalenes 20 and 1,6-heptadiynes 32 with norbornadiene 1 in the presence of ruthenium catalyst produces norbornene derivatives (5α,5aα,9aα,10α)-5,10-diaryl-5,5a,6,9,9a,10-hexahydro-1H-6β,9β- naphtho[b,f:g]acenaphthalenes 21 and (4α,4aα,8aα,9α)-4,9-di(aryl)-2,3,4,4a, 5,8,8a,9-octahydro-1H-5β,8β-methanocyclopenta[b]naphthalenes 36.
Ruthenium complex [RuCl2Cp*]2 is a suitable catalyst. Reaction temperature at 130 oC and a mixture solvent of isopropanol and p-xylene make the reaction more efficient. Based on our optimized reaction conditions, several norbornene derivatives 21 and 36 (15 examples, 34-82 % yield) have been prepared. Their structures have been confirmed by 2D-NMR spectra and X-ray diffraction analysis.
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校內：2011-07-18公開校外：2011-07-18公開